References of "Debuigne, Antoine"
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See detailStudy of the Influence of Pure Ionic Liquids on the Lipase-catalyzed (Trans)esterification of Mannose Based on their Anion and Cation Nature
Galonde, Nadine ULg; Nott, Katherine ULg; Richard, Gaetan ULg et al

in Current Organic Chemistry (2013), 17(7), 763-770

A screening of nine ionic liquids (ILs) has been carried out in order to study the influence of the anion's and cation's nature and structure on the synthesis of mannosyl myristate by (trans ... [more ▼]

A screening of nine ionic liquids (ILs) has been carried out in order to study the influence of the anion's and cation's nature and structure on the synthesis of mannosyl myristate by (trans)esterification catalyzed by Novozym® 435. The best ILs in terms of yield (η) and initial rate (v0) are those based on the TFO- anion. The 24h yield (24h-η) reached 64.9% in [Bmim][TFO] and 70.9% in [Bmpyrr][TFO] by transesterification while it reached 29.7% and 44.5% respectively in each IL by esterification. [Bmpyrr][TFO] based on the pyrrolidinium cation gave the best results although this cation has been rarely used for biocatalysis. This work has thus highlighted a cation that could be further studied in biocatalysis of glycosylated compounds. The study of the relationship between the structure of the ILs and the v0 and η for the biocatalysis of mannosyl myristate showed that the lipase effectiveness is influenced by the anions while the cations have an indirect influence on the interaction strength between Novozym® 435 and the anions. [less ▲]

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See detailPhotochemical properties and activity of water-soluble polymer/C60 nanohybrids for photodynamic therapy
Hurtgen, Marie ULg; Debuigne, Antoine ULg; Hoebeke, Maryse ULg et al

in Macromolecular Bioscience (2013), 13(1), 106-115

Water-soluble star-like poly(vinyl alcohol)/C60 and poly{[poly(ethylene glycol) acrylate]-co- (vinyl acetate)}/C60 nanohybrids are prepared by grafting macroradicals onto C60 and are assessed as ... [more ▼]

Water-soluble star-like poly(vinyl alcohol)/C60 and poly{[poly(ethylene glycol) acrylate]-co- (vinyl acetate)}/C60 nanohybrids are prepared by grafting macroradicals onto C60 and are assessed as photosensitizers for photodynamic therapy. The photophysical and biological properties of both nanohybrids highlight key characteristics influencing their overall efficiency. The macromolecular structure (linear/graft) and nature (presence/absence of hydroxyl groups) of the polymeric arms respectively impact the photodynamic activity and the stealthiness of the nanohybrids. The advantages of both nanohybrids are encountered in a third one, poly[(Nvinylpyrrolidone)- co-(vinyl acetate)]/C60, which has linear grafts without hydroxyl groups, and shows a better photodynamic activity. [less ▲]

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See detailSynthesis of poly(vinyl acetate)-b-poly(vinyl chloride) block copolymers by cobalt-mediated radical polymerization (CMRP)
Piette, Yasmine; Debuigne, Antoine ULg; Bodart, Vinent et al

in Polymer Chemistry (2013), 4(5), 1685-1693

The synthesis of poly(vinyl acetate)-b-poly(vinyl chloride) (PVAc-b-PVC) block copolymers by Cobalt-Mediated Radical Polymerization (CMRP) is investigated for the first time in this paper. A PVAc–Co(acac ... [more ▼]

The synthesis of poly(vinyl acetate)-b-poly(vinyl chloride) (PVAc-b-PVC) block copolymers by Cobalt-Mediated Radical Polymerization (CMRP) is investigated for the first time in this paper. A PVAc–Co(acac)2 macroinitiator is prepared by CMRP using the V-70/Co(acac)2 binary system or a preformed alkylcobalt(III) compound. Then, the block copolymerization occurs in the bulk at 40 °C by the addition of VC. The addition of water to the polymerization medium or the slow generation of alkyl radicals during the whole polymerization is beneficial to the process by consuming part of the excess of deactivator (Co(acac)2) that blocks the polymer chains into the dormant form. Dynamic light scattering (DLS) measurements and AFM analyses evidence that the PVAc-b-PVC forms core–shell micelles in a selective solvent of the PVAc block, i.e. methanol, evidencing the blocky structure of the copolymer. PVAc-b-P(VC-co-VAc) copolymers are also successfully prepared by initiating the radical copolymerization of VC and VAc at 40 °C from a PVAc–Co(acac)2 macroinitiator. [less ▲]

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See detailCobalt-mediated radical (co)polymerization of vinyl chloride and vinyl acetate
Piette, Yasmine; Debuigne, Antoine ULg; Jérôme, Christine ULg et al

in Polymer Chemistry (2012), 3(10), 2880-2891

The cobalt mediated radical polymerization (CMRP) of vinyl chloride (VC) in the presence of bis(acetylacetonato)cobalt(II) (Co(acac)2) as a controlling agent is presented for the first time. Using an ... [more ▼]

The cobalt mediated radical polymerization (CMRP) of vinyl chloride (VC) in the presence of bis(acetylacetonato)cobalt(II) (Co(acac)2) as a controlling agent is presented for the first time. Using an alkyl-Co(III) compound (R0–(CH2–CHOAc)<4–Co(acac)2; R0 = (H3C)2(OCH3)C–CH2–C(CH3)(CN)–) as an initiator, the bulk polymerization under non-isotherm conditions is controlled. 1H NMR spectra of the resulting PVC show that the CMRP process does not significantly affect the level of defects compared to a PVC prepared by a conventional free radical polymerization at the same temperature. Using the same alkyl-cobalt(III) compound, the copolymerization of VC and VAc is controlled at 40 °C provided that enough VAc (about 40 mol%) is present in the polymerization medium to moderate the VC polymerization. In line with reactivity ratios, VC is preferentially incorporated in the polymer at the early stages of the polymerization, leading to copolymers with a high VC content at moderate conversions. This is the first report of a CMRP of VC and of the synthesis of well-defined statistical PVC-co-PVAc copolymers by this technique. [less ▲]

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See detailDesign of novel copolymers by cobalt-mediated radical polymerization of N-vinyl amides
Debuigne, Antoine ULg

Conference (2012, September 21)

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See detailMechanistic investigation and selectivity of the grafting onto C60 of macroradicals prepared by cobalt-mediated radical polymerization
Hurtgen, Marie ULg; Debuigne, Antoine ULg; Gigmes, Didier et al

in Polymer (2012), 53(20), 4353-4358

The grafting mechanism of poly(vinyl acetate) macroradicals prepared by cobalt-mediated radical polymerization onto C60 is investigated. The experimental conditions directly impact the nature and ... [more ▼]

The grafting mechanism of poly(vinyl acetate) macroradicals prepared by cobalt-mediated radical polymerization onto C60 is investigated. The experimental conditions directly impact the nature and stability of the PVAc/C60 adducts. In the presence of residual initiating radicals that can compete with PVAc! macroradicals for addition onto C60, mixtures of PVAc/C60 adducts having between one and eight polymer chains per C60 are formed. PVAc/C60 adducts prepared with low [PVAc]:[C60] ratios may contain weak C60-C60 bonds that further dissociate and account for the instability of the products. The formation of such dimers can be lessened by increasing the temperature from 30 !C to 100 !C. The temperature increase also allows a complete dissociation of the PVAc-Co dormant species into PVAc! macroradicals and an almost quantitative grafting of eight PVAc chains onto C60, leading to well-de!ned C60(PVAc)8 octa-adducts. These results might shed new light on the grafting onto C60 of macroradicals prepared by other CRP techniques. [less ▲]

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See detailUse of new surface active carbohydrate esters for the synthesis of polyhipes in supercritical CO2
Boyère, Cédric ULg; Favrelle, Audrey; Grignard, Bruno ULg et al

Poster (2012, September 10)

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See detailSINGLE-MOLECULE AFM STUDY OF ADHESIVE POLYMERS PREPARED BY COBALT-MEDIATED RADICAL POLYMERIZATION AND NITRONE-MEDIATED RADICAL COUPLING
Willet, Nicolas ULg; Sluysmans, Damien ULg; Delvaux, Cédric ULg et al

Scientific conference (2012, September 10)

Well-defined poly(vinyl acetate) (PVAc) chains prepared by CMRP (cobalt-mediated radical polymerization) were coupled using an alkyne-functional nitrone via NMRC (nitrone-mediated radical coupling).1 In ... [more ▼]

Well-defined poly(vinyl acetate) (PVAc) chains prepared by CMRP (cobalt-mediated radical polymerization) were coupled using an alkyne-functional nitrone via NMRC (nitrone-mediated radical coupling).1 In all the cases, the coupling efficiencies were close to 90% or higher. The polymers mid-chain functionalized with an alkyne group were then reacted with azide-functionalized atomic force microscopy (AFM) tips via copper-catalyzed azide-alkyne cycloaddition (CuAAC). As a result, polymers having a double-branch architecture were linked to AFM tips via a short linker. The structure and the molecular parameters of the polymers were determined by NMR and GPC, whereas the ‘click’ step onto AFM tips was assessed by performing the same CuAAC reaction onto macroscopic surfaces and characterizing them by ATR FT-IR. The adhesive properties of these double-branched polymers were studied by AFM single-molecule force spectroscopy. By performing approach-retraction cycles in solution upon a glass surface, the interaction between single PVAc chains and the surface was investigated. The effect of the double-branch architecture on the adhesion forces was under focus. Setting a residence time of the tip on the surface before retraction was found to have a beneficial influence on the adhesion forces. Signs of multiple interactions acting in parallel were detected in the experimental force-distance traces. [less ▲]

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See detailOrganometallic-mediated radical polymerization of vinyl amides: Effect of metal coordination
Kermagoret, Anthony ULg; Morin, A.; Hurtgen, Marie ULg et al

Poster (2012, September 04)

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See detailOrganometallic-mediated radical polymerization of vinyl amides: Effect of metal coordination
Kermagoret, Anthony ULg; Morin, A.; Hurtgen, Marie ULg et al

Conference (2012, September 04)

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See detailSynthesis of microsphere-loaded porous polymers by combining emulsion and dispersion polymerisations in supercritical carbon dioxide
Boyère, Cédric ULg; Léonard, Alexandre ULg; Grignard, Bruno ULg et al

in Chemical Communications (2012), 48(67), 8356-8358

Highly porous materials were produced by acrylamide polymerisation templated by supercritical CO2-in-water emulsions using new fluorinated glycosurfactants. Properties of the resulting polymer scaffolds ... [more ▼]

Highly porous materials were produced by acrylamide polymerisation templated by supercritical CO2-in-water emulsions using new fluorinated glycosurfactants. Properties of the resulting polymer scaffolds were tuned by performing dispersion polymerisations within their cavities filled with supercritical CO2. [less ▲]

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See detailSynthetic and mechanistic inputs of photochemistry into the bisacetylacetonatocobalt- mediated radical polymerization of n-butyl acrylate and vinyl acetate
Detrembleur, Christophe ULg; Versace, Davy-Louis; Piette, Yasmine et al

in Polymer Chemistry (2012), 3(7), 1856-1866

The input of photochemistry to the Co(acac)2 mediated radical polymerization (CMRP) of n-butyl acrylate and vinyl acetate is investigated for the first time. Upon UV irradiation, photoinitiators are able ... [more ▼]

The input of photochemistry to the Co(acac)2 mediated radical polymerization (CMRP) of n-butyl acrylate and vinyl acetate is investigated for the first time. Upon UV irradiation, photoinitiators are able to initiate the n-butyl acrylate polymerization that remains controlled up to very high molar masses (>4 × 106 g mol−1) with low polydispersities. The photoinitiator as well as the irradiation time must be appropriately chosen to reach acceptable initiator efficiencies while maintaining an optimal control over the polymerization. Laser flash photolysis experiments were then carried out to evidence the addition of alkyl and phosphonyl radicals onto Co(acac)2 and to determine the rate constants (kdeact) of these addition reactions that were still lacking. Finally, both kinetics of polymerization and spin-trapping experiments have evidenced that the C–Co bond at the extremity of the dormant polymer chains can be easily photocleaved. UV irradiation can therefore be considered as an additional lever for tuning the reactivity of the CMRP process mediated by Co(acac)2. [less ▲]

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See detailInterpolymer radical coupling: A toolbox complementary to controlled radical polymerization
Debuigne, Antoine ULg; Hurtgen, Marie ULg; Detrembleur, Christophe ULg et al

in Progress in Polymer Science (2012), 37(7), 1004-1030

The current review focuses on the relevance and practical benefit of interpolymer radical coupling methods. The latter are developing rapidly and constitute a perfectly complementary macromolecular ... [more ▼]

The current review focuses on the relevance and practical benefit of interpolymer radical coupling methods. The latter are developing rapidly and constitute a perfectly complementary macromolecular engineering toolbox to the controlled radical polymerization techniques (CRP). Indeed, all structures formed by CRP are likely to be prone to radical coupling reactions, which multiply the available synthetic possibilities. Basically, the coupling systems can be divided in two main categories. The first one, including the atom transfer radical coupling (ATRC), silane radical atom abstraction (SRAA) and cobalt-mediated radical coupling (CMRC), relies on the recombination of macroradicals produced from a dormant species. The second one, including atom transfer nitroxide radical coupling (ATNRC), single electron transfer nitroxide radical coupling (SETNRC), enhanced spin capturing polymerization (ESCP) and nitrone/nitroso mediated radical coupling (NMRC), makes use of a radical scavenger in order to promote the conjugation of the polymer chains. More than a compilation of macromolecular engineering achievements, the present review additionally aims to emphasize the particularities, synthetic potential and present limitations of each system. [less ▲]

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See detailControlled radical polymerization of halogenated monomers
Bodart, Vincent; Piette, Yasmine; Detrembleur, Christophe ULg et al

Patent (2012)

Process for the preparation of a halogenated polymer comprising a controlled radical polymerization step of at least one monomer containing at least one halogen-carbon bond performed in the presence of an ... [more ▼]

Process for the preparation of a halogenated polymer comprising a controlled radical polymerization step of at least one monomer containing at least one halogen-carbon bond performed in the presence of an organo-cobalt complex, said polymerization step being further carried out in the presence of at least one ligand. [less ▲]

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See detailControlled radical polymerization of halogenated monomers
Bodart, Vincent; Piette, Yasmine; Detrembleur, Christophe ULg et al

Patent (2012)

Process for the preparation of a halogenated polymer comprising a controlled radical polymerization step of at least one monomer containing at least one halogen-carbon bond, performed in the presence of ... [more ▼]

Process for the preparation of a halogenated polymer comprising a controlled radical polymerization step of at least one monomer containing at least one halogen-carbon bond, performed in the presence of an organo-cobalt complex, said polymerization step being further carried out in non-isotherm conditions. [less ▲]

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